Certain 3-aryl-1, 4, 2-oxathiazol-one-5-compounds



United States Patent 3 5 Claims. or: 260-3053! The present invention concerns novel oxathiazol-ones which exhibit strong insecticidal and fungicidal properties and in particular properties which influence plant growth.

3,182,068 Patented May 4, 1965 "ice represents aryl radicals such as phenyl and naphthyl, which may be substituted by alkyl, alkoxy, and alkylmercapto with 1-4 carbon atoms in each case, by the nitro group and also by halogen, particularly by chloride and bromine.

The process according to the invention is preferably carried out in the presence of acid binding agents.

Aqueous alkali metal hydroxides as well as alkali metal carbonates and tertiary amines have proved particularly suitable for this purpose. In addition, it is possible to allow the reaction according to the process to proceed in the presence of inert organic solvents or diluents.

The compounds according to the invention are characterised by good insecticidal and fungicidal properties.

However, the products of the process have a particular Thefhlohydmxhmlc hclds on which the oxathlazol'ones practical significant owing to their pronounced strong 'accol'dmg to the hh are based are h h known" herbicidal activity which they develop on living plants. H they only exhlblt very Weak herblcldal Proper These properties of the oxathiazol-ones obtainable in hes accordance with the invention, which are extremely valu- It 15 an Ohlect of the Fresh/ht lhvehhoh, to Provlde a able in technical application, are evident from the follownovel process for the production of oxathiazol-ones. A ing experimental report further object of h h h i f Provldlflg hovel Some experimental results are summarised below in h Whlch exhlhlt msechclhal funglcldfh as the form of tables which were obtained during the treat- Weh as herhlfhdal Properhesother ohlect? h the mveh' ment of different types of plants after their germination tion are indicated by the followmg description and the (post emergence) examples- The tests are carried out by the normal rocedure in l P It has h found that the novel 3'aryll 4 z'oxathlazo accordance with the post emergence method. The comof U16 formula positions are prepared by taking up the active agent in about 4 times its Weight of dimethylformamide, and by diluting the resultant concentrate with water to give the desired concentrations, with the addition of poly-oxyethyl- I ene benzyl ether as the emulsifying agent.

The resultant corn ositions are s ra ed onto lants wherein Ar represents aryl radlcalsoptionally substituted of the Specified type f their heightpis 1 cm %hree y p h h i and h weeks later, an evaluation of the eifect is made according hibit strong insecticidal, fungicidal, and especially herbito 6 grades where have the significance specified in cldalproheitles'. h h f d h t 1 f the Table I. Results, see Tables Iand Ia.

In addmon It Z t a 9 i fi 9 In order to estimate the herbicidal activity before Fqrmula I are 0 ltame w en aroma 1c 0 y roxamlc germination (pm-emergence), seeds of the different aclds of the forum a 40 plants were sown in ordinary soil and 24 hours later treated %NOH with a composition of 3-(2,6-dichlorophenyl)-1,4,2- ArC oxathiazol-one-S at the stated concentration. The degree of damage or the degree of germination, respectively, was H evaluated after an interval of 3 weeks. During this procewherein Ar has the Same significance as in Formula I, 40 dure, the lndlces 0-5 have the following significance: are reacted with phosgene. 0:119 effect The fact that the oxathiazol-ones according to the inh damage f 0f gTOWth vention exhibit strong biocidal and in particular herbicidal gig gi 225512 0? o l l l gghy r 51 533121 properties 1? Contrast to the prawn-Sly known 59 4' lant s artl d estro "ii afte r e mination or onl 257 droxamic acids, must be regarded as distmctly surprising. P P Y Y- a l y 0 The thiohydroxamic acids to be employed for the gefmlnated process according to the invention are clearly character- 5=P1al1ts Wholly 14111661, 01i100% non-gefmlnated ised by the formula given above. In this, Ar preferably Results, see Table II.

TABLE I Concn. Herbicidal activity when applied againstof ac'tive Product igiini Millet; Beet Oats Cotton Wheat Mustard Tomatoes Beans Iigggg- Cheicg- Grgglndso=o 0.4 5 5 4-5 5 2-3 5 5 5 5 5 c i 0.2 4-5 4-5 4 5 2 5 5 5 5 5 5 0.1 4 4-5 3-1 5 1-2 5 4-5 4 4-5 2 31 SC=O In the above table, the individual indices have the following significance:

0=n0 effect; 1=individual slight smut spots; 2=distinet peripheral smut marks; 3=heavy damage; 4=hali the leaves destroyed; 5=plant is dead.

TABLE Ia Horblcidal activity on application against- Product Concn. of active agent, as Millet Beet Oats Cotton Wheat Mustard Tomatoes Beans percent I NO 4 5 5 4-5 5 5 3-4 4-5 G 0 2 3 5 5 2 4-5 3 2 2 0 1 3 5 4 1 4-5 2 2 2 l S-O=0 Cl NO -G 0.4 4 4 4 1 l 5 3 l l l S =0 Cl OCHa N--0 0.4 5 5 3 5 4 5 O 0.2 4 5 3 5 1 4-5 2 4-5 0.1 5 2 0 4-5 0 3 1 SC=O Cl NO O 4 5 4 4 5 3 5 1 4 CH3 C O 2 5 4 3 2 l 5 0 3 0 1 5 2 2 1 0 4 0 2 SC=O TABLE II g. of 3-(4'-chlorophenyl)- 1,4,2-oxathiazol-one. M.P.

135 C. (after recrystallisation from alcohol).

Cone. (kg/hectare) Millet Beet Oats Cotton Wheat Mustard Example 3 5 5 5 5 5 6 O1 5 5 5 5 5 5 I N-O 5 5 5 4 4 5 2 5 5 3 4 4 -C 0 5 5 0 r 4 The following examples are given for the purpose of illustrating the invention.

Example 1 23 g. of benz-thiohydroxamic acid are dissolved in a solution of 12 g. of sodium hydroxide in 200 ml. of water. Gaseous phosgene is subsequently passed into this mixture at 5-10 C., with external cooling and the simultaneous dropwise addition of a solution of 8 g. of sodium hydroxide in ml. of water until the reaction mixture has an almost neutral reaction. The separated crystals are thereafter filtered off with suction and dried. The yield amounts to 17 g. of 3-phenyl-1,4,2-oxathazol-one-5 of M.P. 96-97 C. (from alcohol).

Example 2 1 5 g. of 4-chlorobenZ-thiohydroxamic acid are dissolved in a solution of 12 g. of sodium hydroxide in 200 ml. of water, and phosgene is passed into this mixture at 5 to 10 C., with external cooling and the simultaneous dropwise addition of a solution of 8 g. of sodium hydroxide in 50 ml. of water until the mixture has a practically neutral reaction. The separated reaction product is filtered off with suction, washed with Water, and dried. Yield: 15

When 15 g. of 3-chlorobenz-thiohydroxamic acid are reacted with phosgene by the method described in Example 2, 12 g. of 3-(3'-chlorophenyl)-1,4,2-oxathiazolone-S of M.P. 68 C. (from alcohol) are obtained.

Example 4 15 g. of 2-chlorobenz-thiohydroxamic acid produce 10 g. of 3-(2-ch1oropheny1)-1,4,2-oxathiazol-one-5 of M.P. 68 C. (from ligroin) by a method analogous to that described in Example 2.

Example 5 5 6 Example 6 4. A compound of the formula When the procedure is analogous to that in Example 2, the following compounds are obtained from the corre- 1--0 I sponding starting materials: 5

5. A compound of the formula N0 01 l -C\ M.P. 138-140 O. W hite spirits. 0 l STC=O Q 1 00113 S- =0 6. A compound of the formula 0 C I 1\'I.P.143145 C. Carbon tetra- Cl G chloride N O S- =0 ligroin. oHio 00m -o l 0 7. A compound of the formula C M.P. l28130 O Carbon tetra- I \S C O chloride. (I31 N 0 o1 00m l %NO om-o M.P. 82-84 0-- White spirits. 1

s 8. A compound of the formula We claim: -O\ 1. A 3-aryl-1,4,2-oxathiazol-one of the formula s OCHK A C References Cited by the Examiner \S C 0 UNITED STATES PATENTS 2,752,357 6/56 Watanabe 260307 in WhlCll Ar stands for a member selected from the group con- OTHER REFERENCES Sistifig 0f P y p y and Substitution P Huisgen et al.: Angew. Chem, vol. 73, pages 656-7 ucts thereof which are substituted by at least one (19 1 member selected from the group consisting of alkyl Ch Ab t a t ol, 56, page 7306g (1962). With Ca atoms, alkOXY with Carbon Chem. Abstracts, vol. 56, page 1571s (Subject Index) atoms, alkylmercapto with 1-4 carbon atoms, the 40 (1962) nitro group, Chl nd br miu Bambas: The Chemistry of Heterocyclic Compounds 2. A compound of claim 1 wherein Ar is substltuted (N Y k, 1952), page 221, P y wherein the Substituentin chlol'ine- Patterson et al.: The Ring Index, Second Edition 3. A compound of the formula (Wa hington, D0,, 1960), page 10,

IRVING MARCUS, Primary Examiner. I NICHOLAS S. RIZZO, WALTER A. MODANCE, 

1. A 3-ARYL-1,4,2-OXATHIAZOL-ONE OF THE FORMULA 